A dramatic effect of double bond configuration in N-oxy-3-aza Cope rearrangements - a simple synthesis of functionalised allenes

Luis F. V. Pinto, Paulo M. C. Gloria, Mario J. S. Gomes, Henry S. Rzepa, Sundaresan Prabhakar and Ana M. Lobo

Web Table 1. B3LYP/6-31G(d) Calculations for the reactions shown in Scheme 5.
TS1 Z-5A (0.0)^a (Digital repository)^b	TS1 E-5A (1.6/0.9)^a (Digital repository,^bTS3^c)

Intermediates
Z-5 7.0 [9.1]^d (Digital repository)	E-5 0.0 [0.0]^d (Digital repository)

[3,3] Sigmatropic rearrangement
TS2 Z-5 20.8 [20.2]^d (Digital repository)	TS2 E-5 27.0 [27.8]^d (Digital repository,TS4^e)

^aRelative solvated free energy, in kcal mol^-1. ^bAn OAI-PMH compliant institutional data repository, providing access to full information about each system, including a checkpoint and logfile file for Gaussian, coordinates in CML form, and METS-based metadata. ^cDigital repository information for TS3. ^dRelative total B3LYP/6-31G(d) energies in mol^-1 [free energy corrected values]. ^eDigital repository information for TS4.